Copolymers of unsaturated amido compounds



Patented June 3, 1952 COPOLYMERS F UNSATURATED AMIDO COlVIPOUNDS EdwardL. Kropa, Old Greenwich, Conn., assignor to American Cyanamid Company,New York, N. Y., a corporation of Maine No Drawing.

Application September 15, 1951, Serial No. 246,883

15 Claims. (01. 260-454) This application is a continuation-in-part ofmy copending application Serial No. 707,043, filed October 31, 1946. andnow abandoned.

This invention relates to polymerizable compositions, to thepolymerization of such compositions to form insoluble resins, and to theproduction of coating compositions, molding compositions, moldedarticles, laminated articles. etc., from the polymerizable compositions.Polymerizable compositions of this invention include a reactive alkydresin and an organic substance, generally a reactive solvent. Uponreaction of thesesubstances, a substantially insoluble resin is formed.

One of the objects of this invention is to prepare improved resins andespecially'to obtain clear and colorless gels.

It is also an object of this invention to provide potentiallypolymerizable solutions which would be stable during storage.

Still another object of this invention is to control the rate ofpolymerization of the reactive mixture, as well as to improve the,properties and characteristics of resulting gels. I

Another object of this invention is to prepare compounds particularlysuitable for use as coating compositions and as components in coatingcompositions.

A further object of the present invention is to prepare moldingcompositions and especially to prepare clear and colorless moldedmaterials.

Another object of this invention is to prepare laminated moldings havinghigh strength and other desirable properties. A still further object ofthis invention is to provide molding compositions suitable for injectionmolding. Other objects will be apparent from the description.

According to the present invention, I have found that substantiallyinsoluble, substantially infusible resins may be prepared by means ofthe chemical reaction or polymerization of a mixture containing a resinpossessing a plurality ofpolymerizably reactive alpha, beta-enalgroups, 1. e.,

and an organic substance which contains an amido group I conjugatedcarbon-to-carbon' double bonds. Such mixtures may be utilizedincoatinsom 2 V positions, in molding compositions, in laminating, in adhesives,in casting compositions, etc.

For the sake of brevity, the organic substances which contain the amidogroup and the polymerizable reactive CH2=C group will be referred toherein as reactive materials or as reactive materials containing theCH2=C group and they are thus to be distinguished from the resins whichpossess a plurality of polymerizably reactive alpha, beta-enal groupsand which will be designated herein as reactive resins or as unsaturatedalkyd resins. Among the reactive resins used in the practice of thisinvention for interaction with reactive materials containing CH2 =Cgroups are those which are derived from alpha, beta unsaturated organicacids and, therefore, contain the reactive groupings present in theseacids. The term acids as used herein is intended to include theanhydrides as well as the acids themselves since the former may be usedinstead of the acid. The term alpha, beta unsaturated organic acid" asusedin the art does not include acids wherein the unsaturated group ispart of an aromaticacting radical as, for example, phthalic acid, andthe same definition isadopted herein.

' Resins used in the practice of the presentinvention are preferablyproduced by the esterification of an alpha, beta unsaturatedpolycarboxylic acid with a polyhydric alcohol, particularly a glycol.Although esterification of the acid with a polyhydric alcohol is perhapsone of the simplest, most convenient ways of obtaining a reactive resin,I am not precluded from using resins otherwise derived from alpha, betaunsaturated 'organic acids. Reactive resins suitable for my inventionare any of those containing a plurality of polymerizably reactive alpha,beta-enal groups.

A reactive resin such as one prepared by esterification of an alpha,beta'unsaturated organic acid and a glycol or other polyhydric alcoholis mixed with a reactive material containing the 'CH2=C group.Upon'adding a polymerization catalyst and subjecting the mixture topolymerization conditions such as, for example, heat, light, or acombination of both, a substantially insoluble, substantially infusibleresin is obtained.

This invention will be described in greater detail in conjunction withthe following specific examples in which the proportions are given inparts by weight. It should be understood that the examples are merelyillustrative, and it is not intended that the scope of the invention belimited to the details therein set forth.

. Erample 1 f glycol fumarate, ethylene diethylene glycol fumarate andethylene glycol fumarate sebacate (4:3:1 molar ratio) ,;-respectively,by mixing the I {components witha "polymerization catalyst in thegamounts' indicated in the following table and 1 1 heating the mixturein an 011 bath maintained at 5 100 C. V 1 7 Gelation Gelation Propertiesof m Time Min. Temp.,0. Casting SOpartsethyleneglycolfuma- 10 95 Clear,soft,L-' V rate sebacate, parts allyl somewhat I5 ,carbamate, 0.25partbenzoyl' v rubberllke peroxide. parts ethylene glycol fuma- 8% 91Do." 7

rate sebacate 20 parts allyl carbamate 0.5 part benzoyl l peroxide. I V

30partsethy1eneglycolfuma- 13 88 Clear, hard, 20' .":=E!ii. .:r. e! ;elx1;9 r

"mate, 0.5 hart EBHZOYI per'-' V i Y oxide .containing -i'n- Jpctivefiller (triphenyl phos-. V

25-parts'etl'iylene diethylene 86 I Clear, Very -gl yeol i ug arete,"25,-part s .hard, frac- 'agy1 ;e;bap;a t q:5 riart" 7 tuied: i 25be1izoylproxide containing I 59% ginactive filler (trip ie yiphp nh la fnpo a 11; s arle -pu ge impact-112 turs aria nasa zarcofnardn sse554. a

nele 're s e astimeaeaeaewsea acid s bradrylamide with :one

ur filler and 2-par'ts of disk mold p heated -to3160?' lC. and il'ftthere A ulyerizd mmture;Zof-..20 lparts' of anel-eatiglycolifuniai'atefsbacate :(4z33 r1--molar ratioigi 10 dngresslliireiojabout 15 minutes. The result 1 e @ua ee -the'appl .Lundbergfierial v 6inow Paten't'f llo. I

hehgoylfheroiiide contaimng 50% f inactiye filler i V n eeliw se ejthsze heig ells nd i l .mteg ratedah his composi onthenfplacedin a f.iparts bfiniethylenebis=acrylainiderand 0.3lparitj56f.

3 held under slight-qn essure in I arver press-.Zfor

3 Fiberglas cloth is well impregnated, the resiir be rfg Bazfcolreadings averagiriggzfii Propylene-hikers" the F iberglas laminate ofExample 4. The result ing anel'is stiff with a Barcol hardness of 35.

. Example 6 Example 3 'is repeatedgusing in place of the methyleneabisj-acrylami'def; methylene bis-meth- -a'c'rylarrlide'i-"pi-epared bystrongaeid condensation of two mols .of methacrylamide with one mole offormaldehyde as described and claimed in the/ ;aiorementioned LundbergPatent No. 2,475,846. e "The resulting molding is uniformly well curecl.

--- Examp1e4 repeated using methylene bis- 'j S ES SSa high modulus inbending and is found to} have a Barcol hardness averaging 51.

Example 8 methacrylamid'e in placegofimethylenerbiseaeryl amide. Ther-esultin'g paper lami'na'te well bonded and. hasa-Bareol l1'ardness oiab'out45 50.

' 67. parts' df diethylehe glyco te;sebacate (65:1 'molar ratio), :33arts-2dr acrymmiue;

- AQvigoro'us reaction occurs,. accompa ie'di by evolution of gas.

'a'n'd the,cured massis porous. f

V V Extt ml'lleifo f 7 To loparts-oidiethyleneglycol:iurnarate seba- 1 r1 1 cate. (6:5:1 molar ratio).,:.-=10 eparts h-f N -butyl acrylam'i'decontaining 0.3 *ipai ta-of .benzoylj'gher -ox'idefdissolved therein areadded. l he :mixture not compatible at room temperature. The dispersion:isoastas;a,flat sheet"imaiglarsV {The resulting -10: ed resinrsheetfiscleargand about-10. 1V V e flamed 1i 14-9.

A'eu stafi'uan homogeneous riiiiiture i's'*made -'of-25-grams'ofNNfdiallylO allyl carb'amaiteand 50 gr amslilf an Unsaturated amyaesmpweueed by reaction oi the follewi ng deactantsiin the spedifiedm'olarramps;

Phthalicanhydride E'rne 'ieationj betwee'n the 'a a 7 e y 1S carriea cutm then senc 0.003% or ydroquinonera'sedion the weight 0 the-alkyd.

To'the'1 xturep of ith aforememionedman bama te andfinsaturate'aalkyd-resin is wade-a 0.5 gram of a polymeriz'ationcatalystcomprising' methyl ethyl ketonehydroperoxide and 40 dimethylcphthalateJ=as.-a solyent therefon;

and, also; 0.2 m1. cobalt nafihthenate..solufiidri,

. which is a xylene solution of cobalt naiihthenate' containing 2%cobalt as-the metal.

diallyl fi=allyrcarbamate:

T Example- 4 is rep'eated -usi-n'gmethylenebis- As the mass'polymeriz'e's' and' sets, it undergoes about a twoioldexpansion I tained after45 minutes heating.

Example 12 Molar ratio Propylene glycol 6.6 Phthalic anhydride 1.1Fumaric acid 5.5

and 1.0 part of the same catalyst used in Example 11 is employed. Thereaction between the alkyd-forming reactants is carried out in thepresence of 0.06% of di-(tert.-butyl) hydroquinone based on the weightof the original reactants forming the alkyd resin.

A sample of the polymerizable composition is heated on a steam bath at100 C. A hard, opaque copolymer of the unsaturated alkyd resin and theN,N-diallyl-O-allyl carbamate is ob- Example 13 A substantiallyhomogeneous mixture is made of 20 grams of N,N-diallyl-O-allyl carbamateand 60 grams of an unsaturated alkyd resin produced by reaction of thefollowing reactants in the specified molar ratios:

. Molar ratio Ethylene glycol 6.6 Phthalic anhydride 1.1 Fumaric acid5.5

The reaction between the alkyd-forming reactants is efiected in thepresence of 0.06% of di- (tert.-butyl) hydroquinone based on the weightheating on a steam bath at 100 C. for 1 hour.

Example 14 A substantially homogeneous mixture is made of 20 grams ofN-allyl-O-allyl carbamate and 60 grams of the same unsaturated alkydresin used in Example 11. To the mixture of the carbamate and theunsaturated alkyd resin is added 1.0 gram of the same polymerizationcatalyst employed in Examples 11, 12 and 13, and 0.2 ml. of the samecobalt solution. The resulting mix- 'ture yields a hard, clear copolymerafter heating for 2 hours on a steam bath at 100 C.

Example 15 I A substantially homogeneous mixture is made by warmingtogether, on a steam bath, with stirring 15 parts of N-allyl-O-allylcarbamate and 35 parts of an unsaturated alkyd resin produced byreaction of the following reactants in the specified molar ratios:

Molar ratio Propylene glycol 6.6 Maleic anhydride 4.0 Phthalic anhydride2.6

I The reaction between the alkyd-forming reactants is carried out in thepresence of 0.008% of hydroquinone based on the weight of the alkyd.

To each of -part portions of the clear, viscous polymerizablecomposition comprising the above mixture are added thereto, in one case(a), 0.2

"part of a solution of 50% benzoyl peroxide in tricresyl phosphate and(b) 0.1 part oi alpha,- alpha'-bisazoisobutyronitrile. Each of the solutions is heated in a reaction vessel on a 102 0. oil bath. Thecomposition of (a) sets to a clear, pale, yellow-green gel in 8 minutes,while the composition of (b) yields a clear, colorless. gel afterheating for 8 minutes. Both of the catalyzed polymerizable compositionsof this example are suitable for use as casting resins.

Ezmmple 16 This example illustrates the preparation ofN,N-diallyl-Oallyl carbamate.

Parts 'Allyl chloroformate 60.0 Diallyl amine 48.5 Calcium oxide 35.0

Water 300.0

The amine is slurried with the lime and water. and the resulting slurryis cooled to 25 C. The allyl chloroformate is added over a period of 45minutes while the temperature is kept between 20 and 27 C. At the end ofthe reaction period the reaction mass is stirred, filtered and thentreated with dilute hydrochloric acid. The filtrate is in two layers,the upper layer being the desired product, while the lower layer is theaqueous phase. These layers are separated. The crude product(N,N-diallyl-O-allyl carbamate) is dried over sodium sulfate and is thendistilled under reduced pressure. N,N-diallyl-O-ally1-carbamate iscollected as the distillate which-boils at 74-77 C. at 2 min. pressure."

Example 17 This example illustrates the preparation of N-allyl-O-allylcarbamate.

Allyl alcohol (dried and distilled) 116:0 Acetonitrile (dried) 313.0

The mixture of the above ingredients isheated under superatmosphericpressure for three hours at C., after which the reaction mass is'filtered. The separated solid contains only a trace of potassiumcyanate. The filtrate is distilled, and the fraction boiling at 61-85 C.under a pressure of 15-025 mm. is collected as crude N-allyl-O-allylcarbamate. The yield of crude product is 68%. This is redistilled andthe purified product is collected as the fraction boiling at 69-73" C.under a pressure of 0.05 mm.

' All of the reactive materials suitable for reac-- tion with a reactiveresin according to my invention are characterized by the presence of theamido group l xm-a-rm,

and

9 I hydrlc alcohol. Examples of these are glycerol, pentaerythritol,etc. Polyhydrlc alcohols containing more than two hydroxyl groups reactvery readily with the alpha, beta unsaturated organic acids.Consequently, it may be preferable to use some monohydric alcohol inconjunction with the alcohols which contain more than two hydroxylgroups or else some monobasic acid may be used.

It is also possible to introduce initially into the resin structure acertain number of groupings of the type CH2=0 through the use ofunsaturated alkyl compounds. v One way of accomplishing this, forexample, is by direct esterification of an unsaturated alcoholcontaining a CHz=C group. Examples of such alcohols are allyl alcoholand methallyl alcohol.

While the reactive resins may be modified in the same general manner asother alkyd resins, it is preferable to have at least 20% polyhydricalcohol in the reactive mixture and at least 25% poly-basic acid in saidreactive mixture. If a monohydric alcohol or a dibasic acid which doesnot contain polymerizably active groups with respect to organicsubstances containing the CH2=C groups be used, the proportion of suchsubstance will depend on the properties required of the polymerizedreactive material-reactive resin mixture. By the use of a relativelylarge proportion of a polymerizably active dibasic acid, e. g. maleic,in the reactive resin, a hard tough polymer is produced upon subsequentreaction of said reactive resin with a reactive material containing theCH2=C group. On the other hand, if the reactive resin is obtained from arelatively small proportion of polymerizably active dibasic acid and arelatively large proportion of acids which do not contain groupspolymerizably active with respect to organic substances containing CH2=Cgroups, a softer and more rubbery resin results upon polymerization witha reactive material containing the CHz=C group. The same effect isproduced by the introduction of other inactive ingredients. By varyingthe ingredients and the proportions of the ingredients, resins maybeobtained having properties desirable for almost any particular use.

The unsaturated alkyd resins employed in accordance with my inventionare preferably those having an acid number not greater than 50, althoughin some cases resins having an acid number as high as 100 may bedesirable. Generally the acid number should be as low as possible, butthis is sometimes controlled by practical considerations of operationsuch as time, temperature and economy.

The resins should be so formulated that the carboxyl groups of the acidsare reacted with the theoretical molar equivalent of the hydroxylgroupsof the alcohols. In this connection it is to be noted that thehydroxyl groups of modifying alcohols as well as the carboxyl groups ofmodifying acids should be included with the hydroxyl groups and carboxylgroups of the principal reactants, the polyhydric alcohol and the alpha,

beta. unsaturated polycarboxylic acid, respectively.

When glycols are reacted with dicarboxylic acids it is preferable thatthe glycol be present in a molar ratio to the acid of not less than 1:2and that the molar ratio of monohydric alcohol to dicarboxylic acid benot greater than 1:1. In most cases it has been found that a molar ratioof monohydric alcohol to dicarboxylic acid of 1:6 produces the bestresults (5.5 mols of glycol 10 being employed in this case). The samegeneral rules apply when polyhydric alcohols other than glycols such aspentaerythritol, dipentaerythritol or polyallyl alcohols are used, orwhen other polycarboxylic acids having more than two carboxylic groupsare used. In other words, the ratio of the monohydric alcohol to thepolycarboxylic acid should preferably be not greater than 1:1 althoughhigher ratios of monohydric alcohol may be employed if desired. However,for optimum results the ratio of monohydric alcohol to polycarboxylicacid should not exceed 1 mol of monohydric alcohol for each carboxylgroup of the polycarboxylic acid in excess of 1. Thus, for example, aresin may be prepared by the reaction of 1 mol of dipentaerythritol with5 mols of fumaric acid and 4 mols of monohydric alcohol.

It it be desirable to introduce lower alkyl groups into the resin, thismay be done by using maleic esters of monohydric alcohols, e. g. ethylmaleate. The alkyl ester will then be united with the resin bypolymerization. This could not be accomplished with the saturated typeof alkyd,

e. g., phthalic acid esters of polyhydric alcohols.

Resins which contain a plurality of alpha, beta enal groups aresensitive to light, heat and polymerizing catalysts. Since oxygen tendsto cause these resins to polymerize, it is desirable that the resinsshould be made in the absence of this substance, especially whencolorless resins are required. The exclusion of oxygen and polymerizingcatalysts is desirable during the preparation of the resin and thepresence of dissolved oxygen in the original reactants is alsopreferably avoided. Moreover, dust and extraneous par-' ticles thatreagents may pick up usually should be removed, especially if colorlessresins aredesired. O-ne manner in which the dissolved gases and otherextraneous impurities may beremoved is through the distillation of theingredients into the reaction chamber in the absence of air.

In order to keep oxygen from contact with the reactants, an inert gassuch as carbon dioxide orinert gas will also carry away at least part ofthe water formed, and toward the end of the reaction it can be used tocarry away the reactants still remaining unreacted. Upon separation ofthe water vapor the used carbon dioxide or other inert gas would beparticularly suitable for making h gh grade colorless resins since anyresidual reactive impurities such as oxygen would have removed in itspassage through the first batch of resin reactants.

The elfect of light is not so important if the reactants are purifiedand the reaction carried on in an inert atmosphere, as outlined above.However, as an added precaution the esterification may be conducted inthe dark. It is also advisable to avoid local overheating, anddiscoloration is minimized if the reaction is conducted below atemperature of about 200 C. To avoid overheating it is advisable toraise the temperature slowly at the beginning, especially if an,anhydride be used since the reaction between an and an alcohol isexothermic.

The following reactive resins are among those which" may be usedaccording tothe process of the present invention with the polymerizablyreanhydride I of catalyst necessary to effect polymerization may be wellabove One of the difliculties in the use of the compositions describedabove is that they are not susceptible to storage in the mixed formbecause polymerization will usually take place even at room temperaturewithin a comparatively short time. Moreover, when it is desired to curethe compositions very rapidly under heat and pressure, the reactionbecomes at times so vigorous that it cannot be controlled. In order toovercome these difliculties it has been found advisable to incorporate asmall proportion of a polymerization inhibitor in the mixture of resinand reactive material. When it is desired to use this mixture, a: smallpercentage of the polymerization catalyst is added sufficient toovercome the effect of the inhibitor as well as to promote thepolymerization. By careful control of the concentrations of inhibitorand catalyst, a uniform product with a good reaction velocity isobtainable. Upon subjection of this mixture to polymerization conditionssuch as heat, light or a combination of both, with or without pressure,

action are phenolic compounds, especially the polyhydric phenols, andaromatic amines. Speciflc examples of this group of inhibitors arehydroquinone, benzaldehyde, ascorbic acid, isoascorbic acid, resorcinol,tannin, sym. di-beta naphthyl-p-phenylene diamine, and phenolic resins.Sulfur compounds are also suitable.

The concentration of inhibitor is preferably low, and I have found thatless than about 1% is usually sufiicient. However, with the preferredinhibitors, I prefer to use only about 0.01% to about 0.1%.

The inhibitor may be incorporated in the reactive resin-reactivematerial combination (either before or after bodying), or it may beadded to the original reactive resin before or during the esterificationof the said reactive resin. By adding the inhibitor before theesterification it is sometimes possible to use an inhibitor which wouldotherwise be substantially insoluble in the reactive resin-reactivematerial composition. By adding the inhibitor to the unesterifiedmixture the inhibitor may become bound into the resin upon subsequentesterification.

The polymerizable compositions of the present invention may bepolymerized in the presence of heat or light, or a combination of both.Ultraviolet light is more effective than ordinary light. The optimumtemperature of conversion depends somewhat on the boiling point of thereactive material and on the pressures used. For example, at atmosphericpressure as in coating and casting operations, a temperature near orabove the boiling point of the reactive material is unsuitable in mostinstances since substantial amounts of the reactive material will belost by evaporation before the reaction between the resin and reactivematerial is complete. Accordingly, a temperature between roomtemperature, about -25 C., and the boiling point is usually employedwhen a polymerization of this nature is carried out. The rate ofpolymerization doubles for about each 10 C. rise in temperature for thisreaction. A temperature is selected which will give a suitable reactionrate and yet not cause er in pressure molding and since the reactivematerial containing the CH2=C group would a 14:11. substantialvolatilization. Obviously it will be necessary to use lower temperaturesif large or very thick pieces are being cast because of the thereforenot be lost so easily. a higher temperature is preferred.

The particular reactive resin, reactive material and catalystcombination is selected according to the type of product desired, takinginto account the solubilities of the reactants as well as the characterof the resulting gels. Some combinations of reactive resins and reactivematerials result in opaque gels while'other give clear If theunsaturated alkyd resin be incompatible with the reactiveamido-material, chemical interaction of the type described cannot occur.Under these conditions, a solvent may be introduced as only reactivematerials containing the CH2=C group which act as solvents is preferred.

The terms compatible on homogeneous as A used in the specification andclaims are intended clear, glass-like and homogeneous.

opacity or colloidal colors result.

to indicate a system, the. constituents of which are uniformlydistributed throughout the whole mass, and when applied to solutions, toindicate that they may be either true solutions or colloidal solutionsas long as they are substantially stable.

When a reactive resin and a reactive material product under theseconditions may be partially translucent or opaque.

The final resin composition is obtained by reacting a resin containingthe alpha, beta enal groups with a reactive material containing thegroup C=CH2. The chemical reaction which is believed to take place is acombination of the reactive material with the resin at the points ofunsaturation, yielding a less unsaturated system which is essentiallyinsoluble and infusible.

' Ordinarily when a resin is dissolved in a solvent,

the changes which occur are physical in nature.

-. The resin may be isolated from the solvent mixture chemicallyunchanged. In the present invention, however, the combination ofthe-reac- Obviously, for. many The end- I tiveimateriali containingthe:.CI Iz,c -group.and lthetreactive 'resin become 'an-insepara'bleentity the" riginalzingredients;.- not -being .;capable'-ofbeingrfemoveda by solvents ."for theroriginal :i-n-

{gredients r I j. Through theflu'se-of a.=small-amount ofreactive l Ialkyd resimdmcon-jimctiomwith;azlargeamountx; 1 ofreactiveimaterial:iicontaining the..CH2;G 1 f groupiwathe finaalcomposition: contains .notv only j the-estengronpingsirwhich-Zwerezoriginally allies-r 110 ;ent-:-;intheizalkydzzresin-gbut :al'so;.:.the:.carbon*to.-

carbommoleculan-bonds which link the reactive lmateriazl'and:.-;thereactivetresin; 1 Through..th use .of a small amount ofresin-aand a; large- 7 I amounteofl reactive/material, .the :compositeresin 1 is no lbngensolublein those inert :solvents where-1 .1 in thereactiveumaterialr-resinified alone woulddissolvevwUnder:longi'exposuregto' the inert sol- Q ventethe fcompositeresin will tend: to imbibe 1a certairtiquanti-tyiof'iinert:solvent,=.but:it does not 0 j possessethe'issolubilitygrof :the:reactive .Lmateriali l 1 activemiaterial :containing:the::.CHz:G tgrou7 alone andmfisthe:softenin g: point'of: theicompositresimform'edithrougltiriteraction oftheresin andjreactivezmaterial'rshowstthat the softening point f. of theflattenrhaszbeenr-xraised;i-w-The softening 1 pointzmay-iberincreasedverytmarkedly dependingf upon:theratioaaofrlesiniusedin:thercomposition'.

1 peratureaas. "well Bras at elevated: temperatures..

1 qu'antita'e 1 amomitz of esineandasmallamountof-reactive .1 material..sflhe secondra cdmpositionawhen fully- 50 lcured'fims'sessesienozsoftening pointz z-Thefifirst and:thimvvarietiessof -'comp0sition when cured maxi; undemhigh'ztemperatures:andpressure, be I madertwfibw slightly i statimay":efmachinedgturnedlohalathep-sand 1 ed andipsflishefdxand usediinzgeneral'asa turnery composition. The absence ofsoftenin rendersoo thematerialrparticularlyf adaptable to' this purpos. in

1 without dangerof softening and gumming tools. 7

1 Moreover, such acompositiommay,

be t nedzinzlargeblocks I 'witheuit.; fille 2;?1 minatedmaterialsas thebond- 1 'ingiagentmadhesives: coating compositions for fuseiimfinishesgforyvood; metals'oriplastics;or in the treahnentioffibrousmaterials;such as paper; O

I" clotl rjrorwleather;::as impregnating agents" for -fi 1broussmateni'als 'asvassistantsxin dyeing,'--etc.-i

.1 advahtageaimthatithe"physical;contour of an ob"- jectmadefof thepolymerized resin: is:not:lost.e throughasolutionz i Comparisonsofthe-isofteningipointiof: there In general-theasofteningepoint of resinshas a: j

' distinctibearingsaon 'theirabehavior. at room teams 5Wherei'itheisoftening pointafis too .low', diificulty l is encounteredin thatrarticlestsmade from then; 3 resim'slowly lose theirzshape; sin Ilarge articles I -the efiect becomesivery moticeable... A softeningpoint whemrtoowhighron theiothermand -resultsl Q in ai composition whichwill not soften'sufficient= 5 1y in:aimold.xiRoughly;-.three .types'ofecompost-1 ftionsslexistziwitlr zrespectfto; the 'ratio of resin to F. 21 reaeti .materiahcontainingxtheGH2:C group;

YFirsts; arge: amountcof reactive material-and: a. sma amount gof:resin; second; substantiali it both ingredients; rthird, "a large"'omposition. .ob tamed r'rom substantial .5 fv 'bothtreact-ivei'material containing groupand: reactiveresinin'the cured E inthaltitiszunflowablegitmay bemachin'ed 1" if desired,

Mygresinsmaybeutilized m5 moldings; with or. r

In hrdeiz ztd'.usetthe-zcomposition for :moldings', i

' a'moldingcomposition.istobtainedtwhich can-then.

- composition may :be bodied and introduced di- 1 rectly-intoa mold andj'polymerizationto a-solid resin conducted in 'onestep. v

.cious. selection" of. the ratio "of reactive material- 7 to reactiveresinna composition-best suited to thes .formationof the .sol-toafgel,an exothermic re-" t'iiresrunzv the hardenin'giof; the' rcompositiozi,Dar.

thematerial mayatheni be placedin aform and; hardenedunder heat.Sheets.of.resinimayt'be twisted; or- 'madeto conform toa pattern.'andxthen subsequently .cured'iin. the .shapedi-formby 'heat1 alone-2. 4One mannerin'which this may. be accomplished is to polymerize the?reactive. resin' andreactive material containinglthe CH2=C zgr'oupwithoucatalysts until the materialisiincompletely"cured By grindingthispartially:polymerizedaizmateria be shaped under heatand pressurex ii To produce moldings -.or; laminated. materials combinations-of:reactive resin and reactivermate' rial containing. the CHz'=C. -'groupmaybe mixedwith oneor more of. the "various fillers, erg. woodfiour,:-wood fiber; paper idust, clay; .diatomaceou earths,zein,=glass:wool; inicag granite .dust',l.silk flock; cotton 'flock;steel wool; silicon. carbide paper, cloth-:of: any fiber includingglass-,usand silica flour,twhite,"black or colored: pigments, etcSuchamixtureszmay :be (partially polymerized ground. and: *m'oljded;.-.O'nw'the :other' hand;- the v The composition of reactive resin andreactiv materialrmay-he used foriimpregnating various I porousobjectsor-it may be employerras.z'a 'coatin'g compositiong 1 If the:polymerizable,compositions are to be molded under low pressure .('e;'.g; 0-'=50-pounds/sq; -in.),: the composition maybe employed withoutbodyingiorpartial-polymerization: I

V The polymerizable; mixture :maysbe introducecl fi in av positive-mold;without any :filler. i In this instance, however,'thereaction.becomesquite exor I g. light transmission, scratch resistance;inden v=- tation"hardness :and are resistance: -By a 1 inch varying needsof industrymay-be fabricated." i Ther methods-by which; the :reactive material:containing the CH2=C group may bemade to i combine arevarioussaHeatjlight or 'catalystsmay' be USBd'iOI" combinations of .these,'or acombina tion of heat; and pressures-Any suitablemethod f of heating may.be used including the application of high frequency :e'lectric fields toinduce heatg I in the reactive mixture' to polymerize the-latter:

During the. transformation to a hard massive l 1 structure, various 3stagesfioccur "which may be roughly: separated as follows: first; *theinduc tion: period iwherein thematerial remains as asol which slowlyincreases 'infviscosity; secondl the-transformation: of the "sol'into-"'agel;' a'nd' third; the hardening of the gelifiDuring'thetransticularly in the casting or molding of large blocks.

Light, when used alone, causes a. relatively long induction period andduring the transformation of the sol to the gel requires cooling toovercome the exothermic reaction, especially when a powerful source oflight is used for final curing, Using heat alone, gelation occursreadily enough at appropriate termperatures but since the gel, whenformed, has poor heat conductivity, fracturing may occur in the laststage. Through the use of heat and catalyst, the reaction may becomeviolent unless the heating is carefully controlled.

Various combinations of these three factors may be used to bring abouthardening of the mass. Mild heating of the reactive resin and reactivematerial containing the CH2 C group, with or without inhibitors, bringsabout a very gradual increase in viscosity which may be controlled quiteeasily and readily. When the solution has taken on an appropriateconsistency, then accelerators may be introduced and heating conductedat a very much lower temperature. Mild heating may first be used and themass then exposed to light. Use of superoxides and light is veryeffective. In other words, through the use of initial heating orbodying, the'induction time may be decreased markedly.

Four types of polymerizable. compositions can, in general, be made upaccording to the present invention. In the first case, both the reactiveresin and the reactive material containing a CH2=C group may be liquid.Alternatively, the reactive resin may be solid and the reactive amidocompound liquid or the resin, may be liquid and the reactive materialsolid. Finally, both components may be solid. All of these types ofcompositions can be used in casting when sufficient heat is supplied torender all of the materials liquid. Similarly, the crystalline materialsmay be melted and while they are in the molten condition, used toimpregnate cloth or fabric. The advantage of using two solid componentsin the resin is that the composition can be mixed with fillers-and thecatalyst and be kept in the solidcondition. Under heat and pressure in amold the crystalline material melts and is cured with the filler. Incoating applications an organic liquid which is capable of dissolvingboth components can be used to dissolve the resinous composition. Afterapplication the volatile organic liquid can be removed.

The wide divergence of the properties of compositions of the presentinvention which contain a reactive resin and a reactive materialcontaining the CH2=O group enables them to be used in. a variety ofdifferent ways. In liquid form or as solutions they may be used asadhesives, impregnating agents, or as surface coatings. Such anadhesive, for example, can be used for bringing diverse substancestogetherwood, metal, glass. rubber. or other resinous compositions suchas phenolic or urea condensation products. .As a surface composition inthe liquid form, softening agents, cellulose ethers or esters could beadded as well as natural or artificial resins, and the hardening broughtabout active resin and this will cause the top surface to dry quicklyupon subsequent polymerization with a reactive material containing theCH2=C group. In this way a coating composition is obtained which driesboth from top and bottom.

The resinous composition, moreover, may be cast or molded and afterhardening may be isolated as a finished product, or it can be cut,turned and polished into the desired finished product. Provided thesurface of the mold is highly polished, the resinous substance acquiresa clear, smooth finish from the mold. The compositions so obtained,being insoluble, are not easily attacked by'solvents and, beinginfusible, may be worked with ordinary woodworking or metal tools. Theartificial mass can be cut, turned on a lathe, polished and sandedwithout superficial softening and streaking.

Obviously, natural resins or other synthetic resins may be admixed withthe resins of this invention in order to obtain products suitable forparticular purposes. Examples of these are shellac, cellulose esters andethers, urea resins, phenolic resins, alkyd resins, ester gum, etc. Theresins of my invention may also be mixed with rubber or syntheticrubber-like products if desired.

Since many of these resins are originally transparent and free of color,they may be colored with suitable dyes to a wide variety of transparentsoft pastel shades. An example of a suitable dye is Sudan IV. Darkershades may be obtained if desired, e..g., with nigrosine.

It may be desirable in some instances to form a, copolymer of one ormore substances containing the group CH2=C and atleast one polymerizableunsaturated alkyd resin and, after, molding or casting this into anydesired shape, to apply a coating of a harder copolymer to the outside,thus obtaining the same effect as is obtained in the metallurgicalfields by case hardening. Similarly, inserts may be filled with a hardresin in order to act as bearing surfaces or for some other purpose.Such coatings or inserts adhere tenaciously and appear to becomeintegral with the original piece. In order to secure the best resultsinnianufacturing such products, it is desirable to first abrade thesurface of the article before the application of the harder film. Duringthe curing operation, the abrasion marks disappear. This treatment isalso of considerable importance since it may be used to refinisharticles which might have been marred in use.

Many of the advantageous properties of the resin resulting from thepolymerization of mixtures containing reactive materials containing theCH2==C group and reactive resins areapparent "from the foregoingdisclosure. Several important advantages are now to be set forth.

In molding and casting operations curing takes place either in thepresence or absence of air very rapidly. This is of great importance incuring large blocks. Other alkyd resins require a very much longer timeto cure in large blocks, i. e. many months, whereas the compositions ofa reactive resin and reactive material containing the CH2=C grou requireonly a few days at the most.

Another important advantage is the fact that if the reactive materialcontaining the CH2=C group acts as the solvent, it combines with theresin leaving no residual solvent and giving no problems as to solventremoval.

One of the outstanding advantages of these

1. A POLYMERIZABLE COMPOSITION COMPRISING A POLYMERIZABLE UNSATURATEDALKYD RESIN CONTAINING A PLURALITY OF POLYMERIZABLY REACTIVE ALPHA,BETA-ENAL GROUPS AND A COMPATIBLE MONOMERIC ALLYL ESTER OF A MEMBER OFTHE GROUP CONSISTING OF CARBAMIC ACID AND MONO-N-SUBSTITUTED CARBAMICACIDS AND DI-N-SUBSTITUTED CARBAMIC ACIDS WHEREIN THE N-SUBSTITUENT ISSELECTED FROM THE GROUP CONSISTING OF ALKYL RADICALS, ALKENYL RADICALS,ALKYLOL RADICALS, ARYL RADICALS AND ARALKYL RADICALS.